US3557204A - Production of arylphosphine halides - Google Patents
Production of arylphosphine halides Download PDFInfo
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- US3557204A US3557204A US621763A US3557204DA US3557204A US 3557204 A US3557204 A US 3557204A US 621763 A US621763 A US 621763A US 3557204D A US3557204D A US 3557204DA US 3557204 A US3557204 A US 3557204A
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- United States
- Prior art keywords
- phosphorus
- reaction
- aryl
- halide
- arylphosphine
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- 150000004820 halides Chemical class 0.000 title abstract description 19
- 238000004519 manufacturing process Methods 0.000 title description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 29
- 150000001502 aryl halides Chemical class 0.000 abstract description 18
- 239000003054 catalyst Substances 0.000 abstract description 13
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 abstract description 11
- 239000000203 mixture Substances 0.000 abstract description 11
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 abstract description 9
- IMDXZWRLUZPMDH-UHFFFAOYSA-N dichlorophenylphosphine Chemical compound ClP(Cl)C1=CC=CC=C1 IMDXZWRLUZPMDH-UHFFFAOYSA-N 0.000 abstract description 6
- 239000011968 lewis acid catalyst Substances 0.000 abstract description 5
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 25
- 238000000034 method Methods 0.000 description 24
- 229910052698 phosphorus Inorganic materials 0.000 description 14
- 239000011574 phosphorus Substances 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 12
- 239000000376 reactant Substances 0.000 description 11
- -1 methylphosphine dibromide Chemical compound 0.000 description 10
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 150000001499 aryl bromides Chemical class 0.000 description 4
- 150000001500 aryl chlorides Chemical class 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 4
- PXRDVIVDFIVDHI-UHFFFAOYSA-N diphenylphosphane;hydrochloride Chemical compound [Cl-].C=1C=CC=CC=1[PH2+]C1=CC=CC=C1 PXRDVIVDFIVDHI-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 239000002841 Lewis acid Substances 0.000 description 3
- GPWHDDKQSYOYBF-UHFFFAOYSA-N ac1l2u0q Chemical compound Br[Br-]Br GPWHDDKQSYOYBF-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910001507 metal halide Inorganic materials 0.000 description 3
- MPXBXLPABFSXGJ-UHFFFAOYSA-N (2-chlorophenyl)phosphane dihydrochloride Chemical compound Cl.Cl.PC1=CC=CC=C1Cl MPXBXLPABFSXGJ-UHFFFAOYSA-N 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 2
- IBSQPLPBRSHTTG-UHFFFAOYSA-N 1-chloro-2-methylbenzene Chemical compound CC1=CC=CC=C1Cl IBSQPLPBRSHTTG-UHFFFAOYSA-N 0.000 description 2
- FUNUTBJJKQIVSY-UHFFFAOYSA-N 2,4-Dichlorotoluene Chemical compound CC1=CC=C(Cl)C=C1Cl FUNUTBJJKQIVSY-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- PQLAYKMGZDUDLQ-UHFFFAOYSA-K aluminium bromide Chemical compound Br[Al](Br)Br PQLAYKMGZDUDLQ-UHFFFAOYSA-K 0.000 description 2
- 150000001501 aryl fluorides Chemical class 0.000 description 2
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 239000002917 insecticide Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- KUXIQKVLTGHSAN-UHFFFAOYSA-N (2-chlorophenyl)phosphane Chemical compound PC1=CC=CC=C1Cl KUXIQKVLTGHSAN-UHFFFAOYSA-N 0.000 description 1
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical class ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- DLKQHBOKULLWDQ-UHFFFAOYSA-N 1-bromonaphthalene Chemical compound C1=CC=C2C(Br)=CC=CC2=C1 DLKQHBOKULLWDQ-UHFFFAOYSA-N 0.000 description 1
- NHPPIJMARIVBGU-UHFFFAOYSA-N 1-iodonaphthalene Chemical compound C1=CC=C2C(I)=CC=CC2=C1 NHPPIJMARIVBGU-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 241001222553 Tatria Species 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- RFQDUXWUYPNMHE-UHFFFAOYSA-N [P].ClC1=C(C=CC=C1)Cl Chemical compound [P].ClC1=C(C=CC=C1)Cl RFQDUXWUYPNMHE-UHFFFAOYSA-N 0.000 description 1
- AQXADGJQAUJFSR-UHFFFAOYSA-N [P].ClC1=CC=CC=C1 Chemical compound [P].ClC1=CC=CC=C1 AQXADGJQAUJFSR-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- CECABOMBVQNBEC-UHFFFAOYSA-K aluminium iodide Chemical compound I[Al](I)I CECABOMBVQNBEC-UHFFFAOYSA-K 0.000 description 1
- 150000001503 aryl iodides Chemical class 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 1
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical class BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- VNFCPJNRQLEUMS-UHFFFAOYSA-N chloro-(2-methylphenyl)phosphane hydrochloride Chemical class Cl.CC1=CC=CC=C1PCl VNFCPJNRQLEUMS-UHFFFAOYSA-N 0.000 description 1
- MVPPADPHJFYWMZ-IDEBNGHGSA-N chlorobenzene Chemical group Cl[13C]1=[13CH][13CH]=[13CH][13CH]=[13CH]1 MVPPADPHJFYWMZ-IDEBNGHGSA-N 0.000 description 1
- 125000000068 chlorophenyl group Chemical group 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- SDJKREQSNPYHJT-UHFFFAOYSA-N dibromo(phenyl)phosphane Chemical compound BrP(Br)C1=CC=CC=C1 SDJKREQSNPYHJT-UHFFFAOYSA-N 0.000 description 1
- HZIWNLZWAHNCCU-UHFFFAOYSA-N dichloro-(2-methylphenyl)phosphane hydrochloride Chemical class Cl.CC1=CC=CC=C1P(Cl)Cl HZIWNLZWAHNCCU-UHFFFAOYSA-N 0.000 description 1
- 125000004188 dichlorophenyl group Chemical group 0.000 description 1
- XSOTVEGLPNWBPO-UHFFFAOYSA-N diphenylphosphane;hydrobromide Chemical compound [Br-].C=1C=CC=CC=1[PH2+]C1=CC=CC=C1 XSOTVEGLPNWBPO-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 125000002346 iodo group Chemical group I* 0.000 description 1
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 1
- XJTQJERLRPWUGL-UHFFFAOYSA-N iodomethylbenzene Chemical class ICC1=CC=CC=C1 XJTQJERLRPWUGL-UHFFFAOYSA-N 0.000 description 1
- SHXXPRJOPFJRHA-UHFFFAOYSA-K iron(iii) fluoride Chemical compound F[Fe](F)F SHXXPRJOPFJRHA-UHFFFAOYSA-K 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 229940102396 methyl bromide Drugs 0.000 description 1
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 1
- 239000012430 organic reaction media Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- WRTMQOHKMFDUKX-UHFFFAOYSA-N triiodide Chemical compound I[I-]I WRTMQOHKMFDUKX-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/52—Halophosphines
Definitions
- the invention relates to a process for the production of arylphosphine halide by reacting an aryl halide with white phosphorous in the presence of a catalytic amount of a Lewis acid.
- Arylphosphine halides are valuable compositions that can be used as plasticizers, as flame retardants, and as re-- action intermediates in the production of a wide variety of useful compositions such as insecticides, fuel and oil additives, and the like.
- arylphosphine halides include the conversion of primary phosphinic acids to arylphosphine halides by reaction with phosphorus trichloride, as disclosed by Frank, J. Org. Chem. 26, 850 (1961). Another prepara tion of arylphosphine halides was disclosed by Becker in U.S. Pat. No.
- the present invention provides a useful and economical process for the production of arylphosphine halides.
- the inventive process comprises reacting an aryl halide with white phosphorus in the presence of a catalytic amount of a Lewis acid.
- the second reactant that is employed in the process of the invention is an aryl halide.
- the aryl halides that are employed can be represented by the formula RX wherein R represents an aryl radical or an alkaryl radical, preferably a hydrocarbon aryl or alkaryl radical, having from 6 up to 10 or more carbon atoms and having a United States Patent valence of n, wherein X represents a halo group, preferably a bromo, chloro, or iodo group, and wherein n represents a number having a value of from 1 to 3.
- aryl halides include chlorobenzene, bromobenzene, iodobenzene, fluorobenzene, o-dichlorobenzene, p-dichlorobenzene, trichlorobenzenes, o-chlorotoluene, mchlorotoluene, 2,4-dichlorotoluene, l-chloronaphthalene, l-bromonaphthalene, bromotoluenes, iodotoluenes, 1- iodonaphthalene, and the like.
- the catalysts that are employed in the process of the invention are metal halide Lewis acids.
- Specific illustrative examples of these catalysts include stannic tetrachloride, titanium tetrachloride, aluminum triiodide, ferric triiodide, aluminum trifiuoride, ferric trifluoride, aluminum trichloride, aluminum tribromide, ferric trichloride, ferric tribromide, and the like.
- the preferred catalysts include ferric trichloride, aluminum trichloride, aluminum tribromide, and ferric tribromide.
- the proportions of the reactants that are employed in the process of this invention are not narrowly critical.
- the mole ratio of white phosphorus (P aryl halide can vary from about l: /2 to 1:60, preferably from about 1:2 to 1:12, and more preferably from about 1:4 to about 1:6.
- the Lewis acid catalyst is employed in small catalytic quantities.
- the catalyst can be employed in a proportion of from about 0.1 weight percent to about 3 weight percent, and preferably from about 0.2 weight percent to about 1.5 weight percent, based upon the total weight of the reactants.
- the process of the invention is carried out at elevated temperatures.
- the exact temperature employed is dependent somewhat upon the particular nature of the aryl halide reactant.-
- the operable temperature range is normally from about 280 C. to about 420 C., preferably from about 300 C. to about 400 C. and more preferably from about 330 C. to 360 C.
- the temperature then can be employed will normally be within the range of from about 200 C. to about 450 C., preferably within the range of from about 250 C. to about 370 C., and more preferably from about 280 C. to about 300 C.
- the temperature range is preferably somewhat below the temperatures indicated for aryl bromides, for example, preferably from about 250 C. to about 290 C.
- the aryl halide is an aryl fluoride
- somewhat higher temperatures than those indicated for aryl chloride should preferably be employed.
- a preferred temperature range when the aryl halide reactant is an aryl fluoride will be from about 400 C. to about 450 C.
- reaction time is dependent, in part, upon factors such as the exact nature of the reactant, the reaction temperature, and the like. For example, reaction times of from about 1 to about 50 hours can be employed, preferably from about 4 to about 26 hours, and more preferably from about 6 to about 12 hours.
- the process of the invention can be carried out, for example, by adding the reactants and catalyst to a suitable reaction vessel and maintaining the mixture at the elevated reaction temperature for a period of time sufficient to produce an arylphosphine halide.
- the reaction can be carried out in an inert, normally liquid, reaction medium such as a high-boiling aliphatic, aromatic or cycloaliphatic hydrocarbon.
- reaction medium such as a high-boiling aliphatic, aromatic or cycloaliphatic hydrocarbon.
- an inert organic reaction medium is entirely optional. It is in general preferred to carry out the reaction under an inert atmosphere of nitrogen, or the like.
- the reaction can be carried out under atmospheric pressure, superatmospheric pressure, or even subatmospheric pressure, which ever is more convenient.
- the exact pressure that will be employed is dictated to a degree by the boiling points of the aryl halide reactant, or by the boiling point of any inert reaction medium that is employed.
- the reaction can be carried out by gently agitating the reactants during the reaction period, and at the close of the reaction period, by cooling the reaction mixture and then separating the products by conventional methods such as by fractional distillation.
- the distillation will preferably be carried out under vacuum because many of the products of the reaction have relatively high boiling points.
- Any suitable conventional reaction vessel can be employed for the process of the invention.
- the equipment should have means for heating, means for agitation, and means for cooling the reaction at the conclusion of the reaction period.
- the process of the invention produces useful arylphosphine halides that are usually a mixture of an arylphosphine dihalide and a diarylphosphine monohalide.
- useful and valuable compositions that can be produced by the process of the invention there can be named phenylphosphine dichloride, diphenylphosphine monochloride, (ochlorophenyl)phosphine dichloride, bis(ochlorophenyl)phosphine monochloride, 1naphthylphosphine bromides, chlorotolylphosphine chlorides, dichlorotolylphosphine chlorides, and many other useful compositions.
- compositions are useful per se as plasticizers and flame retardant additives for many types of plastics such as vinyl chloride polymers, urethane polymers, phenolic resins, and the like.
- the compositions that are produced by the process of the invention are also useful as reaction intermediates for the production of insecticides, lubricant oil additives, fuel additives, and the like.
- EXAMPLE 1 Preparation of phenylphosphine dichloride and diphenylphosphine monochloride from white phosphorus and chlorobenzene Phosphorus (6.3 g.), chlorobenzene (45 g.) and aluminum chloride (0.7 g.) were charged to a glass tube of 12-inch length and 'Ms-inch I.D. After sealing, the tube was heated to about 350 C. in a 3-liter autoclave which was filled with 650 ml. of npropanol and pressurized with 500 pounds of nitrogen. The reaction mixture was kept at that temperature (between 340 and 360 C.) for 8 hours. After cooling in liquid nitrogen, the tube was opened, its contents transferred to a distillation flask and distilled in vacuo.
- Process which comprises reacting an aryl halide of the formula RX wherein R represents an aryl or an alkaryl radical having from '6 to 10 carbon atoms, X represents a halo group, and ri'represents a number having a value from 1 to 3 with white phosphorous in the presence of a metal halide Lewis acid catalyst at an elevated reaction temperature Of a period of time sufficient to produce an arylphosphine halide or an alkarylphosphine halide.
- aryl halide is an aryl chloride, wherein the reaction temperature is in the range of from about 280 to about 420 C., and wherein the catalyst is a halide of aluminum or iron.
- aryl chloride is chlorobenzene, o dichlorobenzene, p dichlorobenzene, o-chlorotoluene, rn-chlorotoluene, 2,4-dichlorotoluene, or l-chloronaphthalene.
- aryl halide is an aryl bromide
- reaction temperature is in the range of from about 200 to about 450 C.
- catalyst is a halide of aluminum or iron.
- metal halide Lewis acid catalyst is ferric trichloride, aluminum trichloride, ferric tribromide, or aluminum tribroinide.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
IT HAS BEEN DISCOVERED THAT ARYLPHOSPHINE HALIDES CAN BE PRODUCED BY REACTING AN ARYL HALIDE WITH WHITE PHOSPHORUS AT ELEVATED TEMPERATURES IN THE PRESENCE OF A LEWIS ACID CATALYST. TO ILLUSTRATE, CHLOROBENZENE IS REACTED WITH WHITE PHOSPHORUS AT 340* TO 350* C. IN THE PRESENCE OF ALUMINUM CHLORIDE CATALYST TO PRODUCE A MIXTURE OF PHENYLPHOSPHINE DICHLORIDE AND DIPHENYLPHOSPHINE CHLORIDE.
Description
3 557 204 PRODUCTION OF ATZYIZPHOSPHINE HALIDES Kurt Weinberg, Upper Saddle River, N.J., assignor to Union Carbide Corporation, a corporation of New York No Drawing. Filed Mar. 9, 1967, Ser. No. 621,763 Int. Cl. C07f 9/52 U.S. Cl. 260543 6 Claims ABSTRACT OF THE DISCLOSURE It has been discovered that arylphosphine halides can be produced by reacting an aryl halide with white phosphorus at elevated temperatures in the presence of a Lewis acid catalyst. To illustrate, chlorobenzene is reacted with white phosphorus at 340 to 350 C. in the presence of aluminum chloride catalyst to produce a mixture of phenylphosphine dichloride and diphenylphosphine chloride.
The invention relates to a process for the production of arylphosphine halide by reacting an aryl halide with white phosphorous in the presence of a catalytic amount of a Lewis acid.
Arylphosphine halides are valuable compositions that can be used as plasticizers, as flame retardants, and as re-- action intermediates in the production of a wide variety of useful compositions such as insecticides, fuel and oil additives, and the like. Heretofore, however, there has been no satisfactory economic method for the production of this class of compositions. To illustrate, some recent preparations of arylphosphine halides include the conversion of primary phosphinic acids to arylphosphine halides by reaction with phosphorus trichloride, as disclosed by Frank, J. Org. Chem. 26, 850 (1961). Another prepara tion of arylphosphine halides was disclosed by Becker in U.S. Pat. No. 3,036,132. This method involved the reaction of phosphorus trichloride with M(AlR where M is an alkali metal and R is aryl. Maier, in Helv. Chi'rn. Actat, 46, 2026 (1963), reported the reaction of elemental phosphorus with bromobenzene at 350 C. to obtain diphenylphosphine bromide and phenylphosphine dibromide, both in very low yield. In U.S. Pat. No. 3,057,917, Maier discloses another method for the production of arylphosphines halide. In this patent, Maier reacts vaporized arylhalide with red phosphorus in the presence of major amounts of'a metallic catalyst such as copper. This patent states that the use of red phosphorus is preferred, thereby implying that other forms of elemental phosphorus can also be used. However, in the paper which was cited above. Maier pointed out that the reaction methyl bromide with white phosphorus produced only traces of methylphosphine dibromide. Thus, it seems apparent that the more economical white phosphorus cannot be used in Maiers process because the yields of desired product are too low. All of the processes described above are relatively undesirable because none is an economical method for producing arylphosphine halides.
The present invention provides a useful and economical process for the production of arylphosphine halides. The inventive process comprises reacting an aryl halide with white phosphorus in the presence of a catalytic amount of a Lewis acid.
White phosphorus is employed as a reactant in this invention. The second reactant that is employed in the process of the invention is an aryl halide. The aryl halides that are employed can be represented by the formula RX wherein R represents an aryl radical or an alkaryl radical, preferably a hydrocarbon aryl or alkaryl radical, having from 6 up to 10 or more carbon atoms and having a United States Patent valence of n, wherein X represents a halo group, preferably a bromo, chloro, or iodo group, and wherein n represents a number having a value of from 1 to 3. Specific illustrative aryl halides include chlorobenzene, bromobenzene, iodobenzene, fluorobenzene, o-dichlorobenzene, p-dichlorobenzene, trichlorobenzenes, o-chlorotoluene, mchlorotoluene, 2,4-dichlorotoluene, l-chloronaphthalene, l-bromonaphthalene, bromotoluenes, iodotoluenes, 1- iodonaphthalene, and the like.
The catalysts that are employed in the process of the invention are metal halide Lewis acids. Specific illustrative examples of these catalysts include stannic tetrachloride, titanium tetrachloride, aluminum triiodide, ferric triiodide, aluminum trifiuoride, ferric trifluoride, aluminum trichloride, aluminum tribromide, ferric trichloride, ferric tribromide, and the like. The preferred catalysts include ferric trichloride, aluminum trichloride, aluminum tribromide, and ferric tribromide.
The proportions of the reactants that are employed in the process of this invention are not narrowly critical. For example, the mole ratio of white phosphorus (P aryl halide can vary from about l: /2 to 1:60, preferably from about 1:2 to 1:12, and more preferably from about 1:4 to about 1:6. The Lewis acid catalyst is employed in small catalytic quantities. For example, the catalyst can be employed in a proportion of from about 0.1 weight percent to about 3 weight percent, and preferably from about 0.2 weight percent to about 1.5 weight percent, based upon the total weight of the reactants.
The process of the invention is carried out at elevated temperatures. The exact temperature employed is dependent somewhat upon the particular nature of the aryl halide reactant.- For example, when an aryl chloride is the reactant, the operable temperature range is normally from about 280 C. to about 420 C., preferably from about 300 C. to about 400 C. and more preferably from about 330 C. to 360 C. When the aryl halide is an aryl bromide, the temperature then can be employed will normally be within the range of from about 200 C. to about 450 C., preferably within the range of from about 250 C. to about 370 C., and more preferably from about 280 C. to about 300 C. When the aryl halide is an aryl iodide, the temperature range is preferably somewhat below the temperatures indicated for aryl bromides, for example, preferably from about 250 C. to about 290 C. When the aryl halide is an aryl fluoride, somewhat higher temperatures than those indicated for aryl chloride should preferably be employed. For example, a preferred temperature range when the aryl halide reactant is an aryl fluoride will be from about 400 C. to about 450 C.
The process of the invention is carried out for a period of time sufiicient to produce an arylphosphine halide. The exact reaction time is dependent, in part, upon factors such as the exact nature of the reactant, the reaction temperature, and the like. For example, reaction times of from about 1 to about 50 hours can be employed, preferably from about 4 to about 26 hours, and more preferably from about 6 to about 12 hours.
The process of the invention can be carried out, for example, by adding the reactants and catalyst to a suitable reaction vessel and maintaining the mixture at the elevated reaction temperature for a period of time sufficient to produce an arylphosphine halide. If desired, the reaction can be carried out in an inert, normally liquid, reaction medium such as a high-boiling aliphatic, aromatic or cycloaliphatic hydrocarbon. However, the use of an inert organic reaction medium is entirely optional. It is in general preferred to carry out the reaction under an inert atmosphere of nitrogen, or the like. The reaction can be carried out under atmospheric pressure, superatmospheric pressure, or even subatmospheric pressure, which ever is more convenient. However, the exact pressure that will be employed is dictated to a degree by the boiling points of the aryl halide reactant, or by the boiling point of any inert reaction medium that is employed. The reaction can be carried out by gently agitating the reactants during the reaction period, and at the close of the reaction period, by cooling the reaction mixture and then separating the products by conventional methods such as by fractional distillation. The distillation will preferably be carried out under vacuum because many of the products of the reaction have relatively high boiling points.
Any suitable conventional reaction vessel can be employed for the process of the invention. The equipment should have means for heating, means for agitation, and means for cooling the reaction at the conclusion of the reaction period.
The process of the invention produces useful arylphosphine halides that are usually a mixture of an arylphosphine dihalide and a diarylphosphine monohalide. Among the useful and valuable compositions that can be produced by the process of the invention there can be named phenylphosphine dichloride, diphenylphosphine monochloride, (ochlorophenyl)phosphine dichloride, bis(ochlorophenyl)phosphine monochloride, 1naphthylphosphine bromides, chlorotolylphosphine chlorides, dichlorotolylphosphine chlorides, and many other useful compositions. These compositions are useful per se as plasticizers and flame retardant additives for many types of plastics such as vinyl chloride polymers, urethane polymers, phenolic resins, and the like. The compositions that are produced by the process of the invention are also useful as reaction intermediates for the production of insecticides, lubricant oil additives, fuel additives, and the like.
The examples which follow illustrate the invention.
EXAMPLE 1 Preparation of phenylphosphine dichloride and diphenylphosphine monochloride from white phosphorus and chlorobenzene Phosphorus (6.3 g.), chlorobenzene (45 g.) and aluminum chloride (0.7 g.) were charged to a glass tube of 12-inch length and 'Ms-inch I.D. After sealing, the tube was heated to about 350 C. in a 3-liter autoclave which was filled with 650 ml. of npropanol and pressurized with 500 pounds of nitrogen. The reaction mixture was kept at that temperature (between 340 and 360 C.) for 8 hours. After cooling in liquid nitrogen, the tube was opened, its contents transferred to a distillation flask and distilled in vacuo.
Yields:
(1) 18.0 g. of phenylphosphine dichloride, B.P.: 50-55" C./0.5 mm. Hg, 49.6% of theory (based on phosphorus) (2) 15.5 g. of diphenylphosphine monochloride, B.P.: l20-122 C./0.5 mm. Hg. 34.7% of theory (based on phosphorus) (3) 8.6 g. of unreacted chlorobenzene all 4 Combined yields of phenylphosphine dichloride and diphenylphosphine monochloride: 84.3% of theory (based on phosphorus).
EXAMPLE 2 Preparation of (o-chlorophenyl)phosphine dichloride and di (o chlorophenyl)phosphine monochloride from white phosphorus and o-dichlorobenzene Phosphorus (6.3 g.), o-dichlorobenzene (60 g.) and ferric chloride (0.9 g.) were charged to a glass tube of 12-inch length and 'Vs-inch I.D. After sealing, the tube was heated to about 326 C. in a 3-liter autoclave which was filled with 650 ml. of n-propanol and pressurized with 500 pounds of nitrogen. The reaction mixture was maintained at this temperature (317-332") for 8 hours.
After cooling in liquid nitrogen the tube was opened, its
contents transferred to a distillation flask and distilled in vacuo.
Yields:
(1) 12.85 g. of o-chlorophenylphosphine dichloride, B.P.: 7l73 C./0.550.65 mm. Hg, 30.0% of theory (based on phosphorus) (2) 9.42 g. of di (9 chlorophenyl)phosphine monochloride, B.P.: 147153 C./O.5 mm. Hg, 16.4% of theory (based on phosphorus) (3) 26.7 g. of unreacted o-dichlorobenzene Combined yields of o-chlorophenylphosphine dichloride-l-di (0 dichlorophenyl)phosphine monochloride:
46.4% of theory (based on phosphorus).
EXAMPLE 3 Preparation of I-naphthylphosphine dibromide and di-(lnaphthyl)phosphine monobromide from white phosphorus and l-bromonaphthalene Phosphorus (6.3 g.), l-bromonaphthalene (86 g.) and anhydrous ferric chloride (0.9 g.) were refluxed under nitrogen in a reaction flask fitted with an air cooled condenser for 6 hours at atmospheric pressure. After cooling to room temperature the reaction mixture was transferred to a distillation kettle and distilled in vacuo.
Yields:
(1) 23.08 g. of I-naphthylphosphine dibromide, M.P.:
7679 0., Yield: 26.2% of theory (based on phosphorus) (2) 13.21 g. of di-(1-naphthyl)phosphine monobromide, M.P. ISO-152 C., B.P. 240 C./0.5 mm., Yield:
18.1% of theory (based on phosphorus) (3) 17.47 g. of unreacted 1-bromonaphthaline Combined yields of l-naphthylphosphine dibromide and di-(l-naphthyl)phosphine bromide: 54.3% of theory (based on phosphorus) EXAMPLES 4 TO 12 The reactions were run in the same equipment as described in Example 1 and also worked up in the same Way. The results are summarized in the following Table I. In order to show the effect of the catalyst on the reaction, a number of experiments were carried out without catalyst (Examples 4, 7, 9 and 11) for comparison with those carried out in the presence of catalysts.
TABLE I Molt ratio of Reaction Yields in Example THRIL, phosphorus: time, percent; Number Arylllalidv Catalyst. C. :u'yllialirlo hours Products of theory 4 o-l iclilorob zc N 318 2 U 1 8 5 wit-W. 318-332 M i:1iaafiitgiasiaaissaaitlzir f;: at
tSashaat???Bi;2;;lf.%ti atl%i?:3;; at 7 W 8 tSsaaaaatiatsisssasar 5 s m-ch1orow1uwc h- 318-332 m 8 {$13213};filfiififligfillgfiigQiliffigi is;
8 tatria;imargar taare; a ttttiriastsrtiaregattas:innate;;; 11
tanimate:Easiestreassess;; 1rhlmmvhflmhmv ll'lililillfillll llllllfilliiiiil?Zfiillliiiiilfjji:1:131:11: 4351 What is claimed is:
1. Process which comprises reacting an aryl halide of the formula RX wherein R represents an aryl or an alkaryl radical having from '6 to 10 carbon atoms, X represents a halo group, and ri'represents a number having a value from 1 to 3 with white phosphorous in the presence of a metal halide Lewis acid catalyst at an elevated reaction temperature Of a period of time sufficient to produce an arylphosphine halide or an alkarylphosphine halide.
2. Process of claim 1 wherein said aryl halide is an aryl chloride, wherein the reaction temperature is in the range of from about 280 to about 420 C., and wherein the catalyst is a halide of aluminum or iron.
3. Process of claim 2 wherein the aryl chloride is chlorobenzene, o dichlorobenzene, p dichlorobenzene, o-chlorotoluene, rn-chlorotoluene, 2,4-dichlorotoluene, or l-chloronaphthalene.
4. Process of claim 1 wherein the aryl halide is an aryl bromide, wherein the reaction temperature is in the range of from about 200 to about 450 C., and wherein the catalyst is a halide of aluminum or iron.
5;Process of claim 4 wherein the aryl bromide is l-bromonaphthalene.
6. Process of claim 1 wherein the metal halide Lewis acid catalyst is ferric trichloride, aluminum trichloride, ferric tribromide, or aluminum tribroinide.
References Cited- Grayson, Organo-Phosphorus Cmpds., International Symposium, Heidelberg, 1964, pp. 193-199.
lVIaier, Chemical Abstracts, vol. 59, p. 14019C.
LORRAINE A. WEINBERGER, Primary Examiner E. J. GLEIMAN, Assistant Examiner
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4857238A (en) * | 1988-04-28 | 1989-08-15 | Nippon Chemical Industrial Co., Ltd. | Manufacturing method for alkyldihalogenophosphines |
US5698736A (en) * | 1997-01-31 | 1997-12-16 | Akzo Nobel Nv | High temperature, catalytic Friedel-Crafts synthesis of benzene phosphorus dichloride |
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1967
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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US4857238A (en) * | 1988-04-28 | 1989-08-15 | Nippon Chemical Industrial Co., Ltd. | Manufacturing method for alkyldihalogenophosphines |
US5698736A (en) * | 1997-01-31 | 1997-12-16 | Akzo Nobel Nv | High temperature, catalytic Friedel-Crafts synthesis of benzene phosphorus dichloride |
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